JP2021505586A - Microbial killing phenylamidine derivative - Google Patents

Abstract

A compound of formula (I) (in the formula, the substituents are as defined in claim 1). In addition, the present invention relates to horticultural chemical compositions containing compounds of formula (I), the preparation of these compositions, and especially of plants by phytopathogenic microorganisms such as fungi, harvested food crops, seeds or non-biological materials. With respect to the use of compounds or compositions in agriculture or horticulture to control, prevent or control ectoparasites.

Description

The present invention relates to, for example, a microbial-killing phenylamidine derivative as an active ingredient having microbial-killing activity, particularly bactericidal and fungicidal activity. The present invention also prepares these phenylamidine derivatives, intermediates useful for the preparation of these phenylamidine derivatives, preparation of these intermediates, horticultural chemical compositions containing at least one phenylamidine derivative, their compositions. Use of phenylamidine derivatives or compositions to control or prevent ectoparalysis by phytopathogenic microorganisms, especially fungi, on plants, harvested food crops, seeds or non-biological materials in the preparation of products and in agriculture or horticulture. Regarding.

Certain bactericidal and killing fungiphenylamidine compounds are described in WO 2000/046184.

Surprisingly, it was found here that certain novel phenylamidine derivatives have advantageous bactericidal and fungicidal properties.

（式中、
Ｒ¹及びＲ²は、Ｃ₁〜Ｃ₄アルキル及びＣ₃〜Ｃ₈シクロアルキルからそれぞれ独立に選択されるか；又は
Ｒ¹及びＲ²は、それらが付着している窒素原子と一緒に、３〜６員飽和環式基を形成し；
Ｒ³は、水素、ハロゲン又はＣ₁〜Ｃ₄アルキルであり；
Ｒ⁴及びＲ⁵は、水素及びＣ₁〜Ｃ₄アルキルからそれぞれ独立に選択されるか；又は
Ｒ⁴及びＲ⁵は、それらが付着している炭素原子と一緒に、カルボニル基（Ｃ＝Ｏ）を形成し；
Ｘは、Ｏ、Ｓ又はＮＣＨ₃であり；
ｎは、０又は１である；）
の化合物並びにその塩、金属錯体、立体異性体及びＮ−オキシドを提供する。 Therefore, the present invention has the formula (I).

(During the ceremony,
R ¹ and R ² are either each independently selected from C ₁ -C ₄ alkyl and C ₃ -C ₈ cycloalkyl; or R ¹ and R ² together with the nitrogen atom to which they are attached, Forming a 3- to 6-membered saturated cyclic group;
R ³ is hydrogen, halogen or C ₁ -C ₄ alkyl;
R ⁴ and R ⁵ are either each independently selected from hydrogen and C ₁ -C ₄ alkyl; or R ⁴ and R ^5, together with the carbon atoms to which they are attached, a carbonyl group (C = O ) Is formed;
X is O, S or NCH ₃ ;
n is 0 or 1;)
And its salts, metal complexes, stereoisomers and N-oxides are provided.

In a second aspect, the present invention provides an agrochemical composition comprising a compound of formula (I).

The compound of formula (I) can be used for controlling phytopathogenic microorganisms. Therefore, in order to control a phytopathologist, the compound of the formula (I) or the composition containing the compound of the formula (I) according to the present invention can be directly applied to the phytopathologist or a habitat of the phytopathologist (particularly the phytopathologist). Can be applied to plants that are susceptible to damage.

Therefore, in a third aspect, the present invention provides the use of a compound of formula (I) or a compound of formula (I) described herein for controlling phytopathogens.

In a further aspect, the invention comprises the compound of formula (I) or the composition comprising the compound of formula (I) described herein, depending on the plant pathologist or the habitat of the plant pathologist (particularly the plant pathologist). Provided are methods for controlling plant pathologies, including steps to apply to vulnerable plants).

The compounds of formula (I) are particularly effective in controlling phytopathogenic fungi.

Therefore, in a further aspect, the invention provides the use of a compound of formula (I) or a compound of formula (I) as described herein for controlling phytopathogenic fungi.

In a further aspect, the present invention comprises the compound of formula (I) or the composition comprising the compound of formula (I) described herein in the phytopathogenic fungus or habitat of the phytopathogenic fungus. Provided is a method for controlling phytopathogenic fungi, which comprises a step of applying to plants particularly vulnerable to phytopathogenic fungi.

If the substituents are indicated to be optionally substituted, this may be because these substituents may have one or more equivalent or different substituents, eg 1 to 4 substituents. It means that it does not have to be. Usually, three or less such optional substituents are present at the same time. Preferably, no more than two such optional substituents are present at the same time (ie, the groups can be optionally substituted with one or two of the substituents labeled "optional"). .. If the "optional substituent" is a larger group, such as cycloalkyl or phenyl, it is most preferred that only one such optional substituent is present. If the groups are indicated to be substituted (eg, alkyl), this includes those groups that are part of other groups (eg, alkyl in alkylthio).

The term "halogen" refers to fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.

Alkyl substituents (alone or as part of larger groups such as alkoxy-, alkylthio-) can be linear or branched. Alkyl can be, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl and the like, depending on the number of carbon atoms listed, either as itself or as part of another substituent. The isomers are, for example, iso-propyl, iso-butyl, sec-butyl, tert-butyl or iso-amyl.

Cycloalkyl substituents can be saturated or partially unsaturated, preferably fully saturated, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

A haloalkyl group (alone or as a larger group, eg, as part of a haloalkyloxy) can contain one or more identical or different halogen atoms, eg CH ₂ Cl, CHCl ₂ , CCl ₃ , CH. _{It can represent 2} F, CHF ₂ , CF ₃ , CF ₃ CH ₂ , CH ₃ CF ₂ , CF ₃ CF ₂ or CCl ₃ CCl ₂ .

Alkoxy means radical-OR, where R is, for example, an alkyl as defined above. Alkoxy groups include, but are not limited to, methoxy, ethoxy, 1-methylethoxy, propoxy, butoxy, 1-methylpropoxy and 2-methylpropoxy.

The presence of one or more asymmetric carbon atoms in a compound of formula (I) means that the compound can be in optical isomeric form, i.e., enantiomeric or diastereomeric. In addition, astrop isomers can be produced by limiting the rotation of single bonds. Formula (I) is intended to include all these possible heterosexual forms and mixtures thereof. The present invention includes all of these possible heterogeneous forms and mixtures thereof according to the compounds of formula (I). Similarly, formula (I) is intended to include all possible tautomers. The present invention includes all possible tautomeric forms of the compounds of formula (I).

In each case, the compound of formula (I) according to the present invention is in free form, oxidized form as N-oxide, or salt form such as, for example, a salt form that can be used agroeconomically.

The N-oxide is an oxidized form of a tertiary amine or an oxidized form of a nitrogen-containing aromatic heterocyclic compound. These are described, for example, in the book "Heterocyclic N-oxides", A. et al. Albini and S. It is described in Pietra, CRC Press, Boca Raton 1991.

Preferred values for R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X and n are as specified below for any combination of these.

Preferably, R ¹ and R ² are independently C _{1 to} C ₄ alkyl.

More preferably, R ¹ and R ² are independently selected from methyl, ethyl and isopropyl, respectively.

Even more preferably, R ¹ is methyl, ethyl or isopropyl and R ² is methyl or ethyl.

Most preferably, R ¹ is ethyl or isopropyl and R ² is methyl.

Preferably, R ³ is a halogen or a C _{1 to} C ₃ alkyl.

More preferably, R ³ is fluoro, chloro or methyl.

Even more preferably, R ³ is chloro or methyl.

Most preferably, R ³ is methyl.

Preferably, R ⁴ and R ⁵ are independently selected from hydrogen and methyl, respectively, or R ⁴ and R ⁵ form a carbonyl group with the carbon atom to which they are attached.

More preferably, R ⁴ and R ⁵ are both hydrogen, or R ⁴ and R ⁵ form a carbonyl group with the carbon atom to which they are attached.

Most preferably, R ⁴ and R ⁵ are both hydrogen.

Preferably, X is O or S.

Most preferably, X is O.

Most preferably, n is 1.

Embodiments of the present invention are provided as defined below.

The first embodiment provides a compound of formula (I) as defined above, or a salt, stereoisomer or N-oxide thereof.

The second embodiment provides the compound according to the first embodiment, or a salt, a stereoisomer or an N-oxide thereof, and in the formula, R ¹ and R ² are independently C _{1 to} C ₄ alkyl.

Embodiment 3 provides a compound according to Embodiment 1 or 2, or a salt, stereoisomer or N-oxide thereof, wherein R ³ is a halogen or a C _{1 to} C ₃ alkyl in the formula.

Embodiment 4 provides a compound according to any one of Embodiments 1, 2 or 3, or a salt, stereoisomer or N-oxide thereof thereof, in which R ⁴ and R ⁵ are derived from hydrogen and methyl, respectively. Selected independently, or R ⁴ and R ⁵ form a carbonyl group with the carbon atoms to which they are attached.

Embodiment 5 provides a compound according to any one of embodiments 1, 2, 3 or 4, or a salt, stereoisomer or N-oxide thereof, wherein X is O or S in the formula.

Embodiment 6 provides a compound according to any one of Embodiments 1, 2, 3, 4, or 5, or a salt, stereoisomer or N-oxide thereof, wherein R ¹ and R ² are represented in the formula. It is independently selected from methyl, ethyl and isopropyl.

Embodiment 7 provides a compound according to any one of Embodiments 1, 2, 3, 4, 5, or 6, or a salt, stereoisomer or N-oxide thereof, wherein R ³ is fluoro in the formula. , Chloro or methyl.

Embodiment 8 provides a compound according to any one of Embodiments 1, 2, 3, 4, 5, 6, or 7, or a salt, stereoisomer or N-oxide thereof, wherein R ⁴ and N-oxide are provided. R ⁵ is both hydrogen, or R ⁴ and R ⁵ form a carbonyl group with the carbon atom to which they are attached.

Embodiment 9 provides a compound according to any one of embodiments 1, 2, 3, 4, 5, 6, 7, or 8, or a salt, stereoisomer or N-oxide thereof, wherein R ¹ is methyl, ethyl or isopropyl and R ² is methyl or ethyl.

Embodiment 10 provides a compound according to any one of Embodiments 1, 2, 3, 4, 5, 6, 7, 8 or 9, or a salt, stereoisomer or N-oxide thereof, in the formula. , R ³ is chloro or methyl.

The eleventh embodiment provides a compound according to any one of the first, second, third, fourth, fifth, sixth, seventh, eighth, ninth or tenth embodiments, or a salt, stereoisomer or N-oxide thereof. Among them, R ¹ is ethyl or isopropyl and R ² is methyl.

Embodiment 12 provides a compound according to any one of Embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, or a salt, stereoisomer or N-oxide thereof. , In the formula, R ³ is methyl.

Embodiment 13 comprises a compound according to any one of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, or a salt, stereoisomer or N-oxide thereof. Provided, in the formula, R ⁴ and R ⁵ are both hydrogen.

Embodiment 14 is a compound according to any one of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, or a salt, stereoisomer or N-is thereof. Oxide is provided, where n is 1 in the formula.

Embodiment 15 is a compound according to any one of embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, or a salt, stereoisomer or a salt thereof. N-oxide is provided, where X is O in the formula.

The preferred group of compounds according to the present invention are those of formula (I-1), which are compounds of formula (I) (in the formula,
R ¹ and R ² are independently C _{1 to} C ₄ alkyl;
R ³ is a halogen or C _{1 to} C ₃ alkyl;
R ⁴ and R ⁵ are independently selected from hydrogen and methyl, respectively, or R ⁴ and R ⁵ form a carbonyl group with the carbon atom to which they are attached;
X is O, S or NCH ₃ ;
n is 0 or 1);
Or its salt, stereoisomer or N-oxide.

One group of compounds according to this embodiment is a compound of formula (I-1a) which is a compound of formula (I-1), in which X is O.

Another group of compounds according to this embodiment is a compound of formula (I-1b) which is a compound of formula (I-1), in which X is S.

Another group of compounds according to this embodiment is a compound of formula (I-1c) which is a compound of formula (I-1), in which X is NCH ₃ .

A further preferred group of compounds according to the invention are those of formula (I-2), which are compounds of formula (I) (in the formula,
R ¹ and R ² are independently selected from methyl, ethyl and isopropyl, respectively;
R ³ is fluoro, chloro or methyl;
R ⁴ and R ⁵ are both hydrogen, or R ⁴ and R ⁵ form a carbonyl group with the carbon atom to which they are attached;
X is O, S or NCH ₃ ;
n is 0 or 1);
Or its salt, stereoisomer or N-oxide.

One group of compounds according to this embodiment is a compound of formula (I-2a) which is a compound of formula (I-2), in which X is O.

Another group of compounds according to this embodiment is a compound of formula (I-2b) which is a compound of formula (I-2), where X is S.

Another group of compounds according to this embodiment is a compound of formula (I-2c) which is a compound of formula (I-2), in which X is NCH ₃ .

A further preferred group of compounds according to the invention are those of formula (I-3), which are compounds of formula (I) (in the formula,
R ¹ is methyl, ethyl or isopropyl and R ² is methyl or ethyl;
R ³ is chloro or methyl;
R ⁴ and R ⁵ are both hydrogen, or R ⁴ and R ⁵ form a carbonyl group with the carbon atom to which they are attached;
X is O, S or NCH ₃ ;
n is 0 or 1);
Or its salt, stereoisomer or N-oxide.

One group of compounds according to this embodiment is a compound of formula (I-3a) which is a compound of formula (I-3), in which X is O.

Another group of compounds according to this embodiment is a compound of formula (I-3b) which is a compound of formula (I-3), where X is S.

Another group of compounds according to this embodiment is a compound of formula (I-3c) which is a compound of formula (I-3), in which X is NCH ₃ .

A further preferred group of compounds according to the invention are those of formula (I-4), which are compounds of formula (I) (in the formula,
R ¹ is ethyl or isopropyl and R ² is methyl;
R ³ is methyl;
R ⁴ and R ⁵ are both hydrogen;
X is O or S;
n is 0 or 1 (preferably n is 1);
Or its salt, stereoisomer or N-oxide.

One group of compounds according to this embodiment is a compound of formula (I-4a) which is a compound of formula (I-4), in which X is O.

Another group of compounds according to this embodiment are compounds of formula (I-4b), which are compounds of formula (I-4), where X is S.

Ｎ−エチル−Ｎ’−［５−ヒドロキシ−２−メチル−４−［２−（トリフルオロメチル）テトラヒドロフラン−２−イル］フェニル］−Ｎ−メチル−ホルムアミジン；

Ｎ’−［５−ヒドロキシ−２−メチル−４−［２−（トリフルオロメチル）テトラヒドロフラン−２−イル］フェニル］−Ｎ−イソプロピル−Ｎ−メチル−ホルムアミジン；

Ｎ’−［２−クロロ−５−ヒドロキシ−４−［２−（トリフルオロメチル）テトラヒドロフラン−２−イル］フェニル］−Ｎ−エチル−Ｎ−メチル−ホルムアミジン；

Ｎ−エチル−Ｎ’−［５−ヒドロキシ−２−メチル−４−［４−オキソ−２−（トリフルオロメチル）テトラヒドロフラン−２−イル］フェニル］−Ｎ−メチル−ホルムアミジン；

Ｎ−エチル−Ｎ’−［５−ヒドロキシ−２−メチル−４−［２−（トリフルオロメチル）テトラヒドロチオフェン−２−イル］フェニル］−Ｎ−メチル−ホルムアミジン；

Ｎ−エチル−Ｎ’−［５−ヒドロキシ−２−メチル−４−［２−（トリフルオロメチル）オキセタン−２−イル］フェニル］−Ｎ−メチル−ホルムアミジン
である。 Specific preferred compounds of formula (I) are

N-Ethyl-N'-[5-Hydroxy-2-methyl-4- [2- (trifluoromethyl) tetrahydrofuran-2-yl] phenyl] -N-methyl-formamidine;

N'-[5-Hydroxy-2-methyl-4- [2- (trifluoromethyl) tetrahydrofuran-2-yl] phenyl] -N-isopropyl-N-methyl-formamidine;

N'-[2-Chloro-5-Hydroxy-4- [2- (trifluoromethyl) tetrahydrofuran-2-yl] phenyl] -N-ethyl-N-methyl-formamidine;

N-Ethyl-N'-[5-Hydroxy-2-methyl-4- [4-oxo-2- (trifluoromethyl) tetrahydrofuran-2-yl] phenyl] -N-methyl-formamidine;

N-Ethyl-N'-[5-Hydroxy-2-methyl-4- [2- (trifluoromethyl) tetrahydrothiophen-2-yl] phenyl] -N-methyl-formamidine;

N-Ethyl-N'-[5-Hydroxy-2-methyl-4- [2- (trifluoromethyl) oxetane-2-yl] phenyl] -N-methyl-formamidine.

The compounds according to the invention have, among other things, an advantageous level of biological activity for protecting plants against diseases caused by fungi, or excellent properties for use as an agrochemical active ingredient (eg, high biological properties). It can have any number of benefits, including activity, favorable activity spectrum, high safety profile, improved physicochemical properties or high biodegradability).

Specific examples of the compound of formula (I) are illustrated in Tables 1 to 4 below.

の化合物を提供し、式中、それぞれ、Ｒ²、Ｒ³、Ｘ及びｎは、表Ｐ（下記）において定義している通りであり、Ｒ⁴及びＲ⁵は、表１〜４において定義している通りである。 Each of Tables 1 to 4 following Table P below has formula (IA) of 48.

R ² , R ³ , X and n are defined in Table P (below), respectively, and R ⁴ and R ⁵ are defined in Tables 1 to 4, respectively. That's right.

Thus, Table 1 treats the compounds of formula (IA) of 48 individually, and for each row of Table P in the formula, R ⁴ and R ⁵ are as defined in Table 1; and so on. In addition, Table 2 treats the compounds of formula (IA) of 48 individually, where for each row of Table P, R ⁴ and R ⁵ are as defined in Table 2; Table 3 and The same applies to 4.

を有する。 Table 1: This table discloses compounds 1.01 to 1.48 of formula IA, in which R ⁴ and R ⁵ are both hydrogen and the variables R ² , R ³ , X. And n have the specific meanings shown in the corresponding columns of Table P. For example, compound 1.01 has the following structure:

Have.

Table 2: This table discloses compounds of formula IA of 48 from 2.01 to 2.48, in which R ⁴ and R ⁵ are both methyl and the variables R ² , R ³ , X. And n have the specific meanings shown in the corresponding columns of Table P.

Table 3: This table discloses compounds 3.01 to 4.48 of formula IA, in which R ⁴ and R ⁵ are both ethyls and the variables R ² , R ³ , X. And n have the specific meanings shown in the corresponding columns of Table P.

Table 4: This table discloses compounds of formula IA of 48 4.01-4.48, in which R ⁴ and R ⁵ together form a carbonyl group and the variables R ² , R ³ , X and n have the specific meanings shown in the corresponding columns of Table P.

The compounds of the present invention can be made as shown in the scheme below, where the definition of each variable is as defined above for the compound of formula (I) unless otherwise stated. ..

Compounds of formula (I) ^{(wherein, R 1, R 2, R} 3, R 4, R 5, X and n are as defined for formula (I)) by several known methods The compounds of formula (II) can be obtained by conversion of the compounds of formula (II, where R ³ , R ⁴ , R ⁵ , X and n are as defined for formula (I)), among these methods. The most widely used ones are:
a) In an organic solvent, for example toluene or methanol, at a temperature of 0 ° C to 100 ° C, the compounds of formula (III-a) (in the formula, R ¹ and R ² are as defined for formula (I). Yes, R ⁶ is treated with C _{1 to} C ₄ alkyl).
b) Treatment with an orthoester of formula (III-b) (where R ⁶ is C _{1 to} C ₄ alkyl) in an organic solvent, eg, methanol, at a temperature of 20 ° C to 100 ° C, and Subsequent treatment with amines of formula (III-c), where R ¹ and R ² are as defined for formula (I).
c) Formamides of formula (III-d) in an inert solvent, eg, dichloromethane, at a temperature of −20 ° C. to 40 ° C. (wherein R ¹ and R ² are as defined for formula (I)). There is), and treatment with an activator, such as POCl ₃ .

This is shown in Scheme 1 below.
Scheme 1

Compounds of the formula (II) (wherein, R ^3, X and n are as defined for formula (I), R ⁴ and R ⁵ are hydrogen) is under reducing conditions, for example, by catalytic hydrogenation, the compound of formula (IV) (wherein, R ^3, X and n are as defined for formula (I)) can be obtained by conversion. This is shown in Scheme 2 below.
Scheme 2

Compounds of formula (IV) (wherein, R ^3, X and n are as defined for formula (I)) is due to a transition metal catalyst system under the conditions of olefin metathesis, the compound of formula (V) ( In the formula, R ³ , X and n can be obtained by the transformation of formula (I)). This is shown in Scheme 3 below.
Scheme 3

Compounds of formula (V) (wherein R ³ and X are as defined for formula (I) and n is 1) are compounds of formula (VII) (in formula, R ⁷ is: It can be obtained by conversion of compounds of formula (VI), with halogens (preferably chloro or bromo) and with bases, where R ³ and X are as defined for formula (I). it can. This is shown in Scheme 4 below.
Scheme 4

Alternatively, compounds of formula (I) ^{(wherein, R 1, R 2, R} 3, X and n are as defined for formula (I), R ⁴ and R ⁵ are hydrogen) is , For example, by catalytic hydrogenation under reducing conditions (where R ¹ , R ² , R ³ , X and n are as defined for formula (I)) of formula (VIII). It can be obtained by conversion. This is shown in Scheme 5 below.
Scheme 5

Compounds of the formula (VIII) ^{(wherein, R 1, R 2, R} 3, X and n are as defined for formula (I)) is due to a transition metal catalyst system under the conditions of olefin metathesis, compounds of formula (IX) ^{(wherein, R 1, R 2, R} 3, X and n are as defined for formula (I)) can be obtained by conversion. This is shown in Scheme 6 below.
Scheme 6

Compound (wherein, R ^1, R ^2, R ³ and X are as defined for formula (I), n is 1 a is) of the formula (IX) is a compound of formula (VII) (wherein Among them, R ⁷ is a compound of formula (X) by halogen, preferably chloro or bromo) and by base (in the formula, R ¹ , R ² , R ³ and X are for formula (I). It can be obtained by the conversion (as defined). This is shown in Scheme 7 below.
Scheme 7

The compound of formula (X) (in the formula, R ¹ , R ² , R ³ and X are as defined for formula (I)) is the compound of formula (XII) (in the formula, R ⁸ is MgBr. Or Li), which can be obtained by conversion of the compound of formula (XI) (where R ¹ , R ² , R ³ and X are as defined for formula (I)). This is shown in Scheme 8 below.
Scheme 8

Compounds of formula (XI) (wherein R ¹ , R ² and R ³ are as defined for formula (I) and X is O) are due to compounds of formula (XIV) and are strong. Compounds of formula (XIII) with bases such as butyllithium (where R ¹ , R ² and R ³ are as defined for formula (I), where R ⁷ is halogen, preferably bromo or It can be obtained by the conversion of iodo). This is shown in Scheme 9 below.
Scheme 9

Compounds of formula (XIII) (wherein, R ^1, R ² and R ³ are as defined for formula (I), R ⁷ is halogen, preferably bromo or iodo), the number Obtained by conversion of a compound of formula (XV) by the known method of formula (where R ³ is as defined for formula (I) and R ⁷ is halogen, preferably bromo or iodine). The most widely used of these methods are as follows.
a) In an organic solvent, for example toluene or methanol, at a temperature of 0 ° C to 100 ° C, the compounds of formula (III-a) (in the formula, R ¹ and R ² are as defined for formula (I). Yes, R ⁶ is treated with C _{1 to} C ₄ alkyl).
b) Treatment with an orthoester of formula (III-b) (where R ⁶ is C _{1 to} C ₄ alkyl) in an organic solvent, eg, methanol, at a temperature of 20 ° C to 100 ° C, and Subsequent treatment with amines of formula (III-c), where R ¹ and R ² are as defined for formula (I).
c) Formamides of formula (III-d) in an inert solvent, eg, dichloromethane, at a temperature of −20 ° C. to 40 ° C. (wherein R ¹ and R ² are as defined for formula (I)). There is), and treatment with an activator, such as POCl ₃ .

This is shown in Scheme 10 below.
Scheme 10

Compounds of formula (XV) (in which R ³ is as defined for formula (I) and R ⁷ is halogen, preferably bromo or iodine) are halogenating agents such as bromine. It can be obtained by conversion of a compound of formula (XVI) with N-bromosuccinimide or N-iodosuccinimide (where R ³ is as defined for formula (I)). This is shown in Scheme 11 below.
Scheme 11

The compounds of formula (XVI), in which R ³ is as defined for formula (I), are of formula under reducing conditions, such as by catalytic hydrogenation or under conditions of Bechamp reaction. It can be obtained by conversion of the compound of (XVII), in which R ³ is as defined for formula (I). This is shown in Scheme 12 below.
Scheme 12

The compounds of formula (XVII), in which R ³ is as defined for formula (I), are of the formula by methyl bromide or methyl iodide and by bases such as sodium hydride or potassium carbonate. It can be obtained by conversion of the compound of (XVIII), in which R ³ is as defined for formula (I). This is shown in Scheme 13 below.
Scheme 13

Certain intermediates described in the above scheme are novel and thus constitute a further aspect of the invention.

The compound of formula (I) is an active ingredient in the agricultural sector and related fields of use, for example, for controlling plant pests or non-biological materials, and controlling spoilage microorganisms or organisms that are potentially harmful to humans. Can be used as. The new compounds are outstanding due to their excellent activity at low doses, their excellent plant tolerance, and their environmental safety. They have highly useful therapeutic, prophylactic and osmotic transfer properties and can be used to protect a large number of cultivated plants. The compounds of formula (I), on the other hand, simultaneously to inhibit or eliminate pests that occur in plants or parts of plants (fruits, flowers, leaves, stems, tubers, roots) of different crops of useful plants. These parts of later growing plants can also be used, for example, to protect them from phytopathogenic microorganisms.

It is also possible to use the compound of formula (I) as a bactericidal / fungicide. As used herein, the term "bactericidal and fungicidal agent" means a compound that controls, denatures or prevents the growth of fungi. The term "bactericidal and fungicidally effective amount" means the amount of such a compound or a combination of such compounds that can have an effect on the growth of the fungus. Control or degenerative effects include all deviations from natural development such as death, delay, etc., and prevention includes barriers or other defense formation in plants to prevent fungal infections.

A powder coating agent for treating plant breeding materials such as seeds such as fruits, tubers or grains or plant cuttings (eg rice) for protection against fungal infections occurring in the soil and phytopathogenic fungi. It is also possible to use the compound of the formula (I). This breeding material can be treated with a composition comprising a compound of formula (I) prior to planting: for example, the seeds can be powdered before sowing. The compounds of formula (I) can also be applied (coated) to grains by impregnating the seeds into a liquid formulation or by coating the seeds with a solid formulation. The composition can also be applied to the planting site when the reproductive material is planted, for example to the sowing groove during sowing. The present invention also relates to a method for treating such a plant breeding material and the plant breeding material thus treated.

Further, the compound according to the present invention can be used for controlling fungi in related fields such as protection of industrial materials including wood and wood-based industrial products, food storage and hygiene management.

In addition, the present invention can be used to protect non-biomaterials such as timber, wallboards and paints from the action of fungi.

A compound of formula (I) containing these and a bactericidal / fungicidal composition can be used to control plant diseases caused by a wide range of fungal phytopathogens. They are effective in controlling a wide range of plant diseases such as leaf pathogens in ornamental crops, lawns, vegetables, crops, cereals and fruit crops.

Fungi and fungal mediators of these diseases, as well as phytopathogenic bacteria and viruses that can be controlled are, for example:
Absidia corymbifera, Alternaria spp, Aphanomyces spp, Ascochyta spp, A. cerevisiae spp, A. Flabus, A. flavus. A. fumigatus, A. A. nidulans, A. nidulans. Nigger, A. A species of Aspergillus spp., Including A. terrus, A. Aureobasidium spp., Aureobasidium spp., Blastomycosis dermatidis, Blumeria glaminis, Blemeria braminis, Bremi lactuca, including A. pullulans. B. dothidea, B. B. obtusa, a species of the genus Botryosphaeria (Botryosphaeria spp.), B. et al. A species of the genus Botrytis spp., Including B. cinerea, C.I. Albicans, C. albicans. C. glabrata, C.I. C. krusei, C.I. C. lusitaniae, C.I. C. parapsilosis, C.I. C. tropicalis, a species of the genus Candida (Candida spp.), Cephaloascus fragrances, a species of the genus Seratocystis (Ceratocytis spp), C.I. A species of the genus Cercospora (Cercospora spp.), A species of the genus Cercosporium (Cercosporium spp), a species of the genus Cladosporium (Cladosporium spp), Cladosporium spruprea (Cladosporium spp), Cladosporium sp.
Coccidioides imitis, a species of the genus Cochliobolus (Cochliobolus spp), C.I. Colletotrichum spp., A species of the genus Colletotrichum, including C. musae,
Cryptococcus neoformans, a species of the genus Diaporthe (Diaporthe spp), a species of the genus Didymela (Didimela spp), a species of the genus Drexlera (Drechslera spp), a species of the genus Elsinoë (Els)
A species of the genus Epidermophyton (Epidermophyton spp), Erwinia amylovora, E. coli. Erysiphe spp., Erysiphe spp., Containing E. cichoracealum,
Euchipa lata, F. et al. F. culmorum, F. Graminearum, F. zebra F. Langsetiae, F. F. moniliforme, F. F. oxysporum, F. oxysporum, F. oxysporum. F. proliferatum, F. F. subglutinans, F. subglutinans, F. A species of the genus Fusarium (Fusarium spp.) Including Solani, Gaeumanomyces graminis, Gibberella fujikuroi, Groeodespomigena (Gloodespomigena) Gloeosporium musumarum, Glomerella chingulate, Guignardia bidwelli, Gymnosporangium juniperi-Virginiane (Gymnosporium genus) Helminthosporium (Gymnosporium genus) Helminthosporium spp), a species of the genus Hemileia spp), H. et al. One of the genus Histoplasma (Histoplasma spp.), Laetisaria fuciformis, Leptographium lindbergi (Leptographium lindberg), Lebeila, including capsulatum. Lofodermium sedithiosum, Microdochium nivale, Microsporum spp, Monilinia spp, Monilinia spp, Mucor leaf spp Disease fungus (M. graminicola), M. Mycosphaerella spp., Mycosphaerella spp., Oncobasidium theobromaeon, Ophiostoma picea, Ophiostoma picea, paracodice, parapicea, parapicea. .. Digitatum, P. digitatum, P. digitatum. A species of the genus Penicillium (Penicillium spp.) Including Italicum, a species of the genus Petriellidium (Petriellidium spp), P. et al. P. maydis, P. P. filippinensis and P. Phialophora spora spp., Phialophora spp, Phialophora nodolum, Phialophora phopsi, Phialophora pasi, Phialophora spi, Phialophora spp., Phialophora spp., Phialophora sp. Phialinus ignialus, Phialophora spp, Phoma spp, Phomopsis viticola, P. et al. Phytophthora spp., A species of the genus Phytophthora, including P. infestans. Halstedi, P. halstedi, P. A species of the genus Plasmopara (Plasmopara spp.) Including P. viticola, a species of the genus Pleospora (Pleospora spp.) Pseudomonas, Pseudomonas, Pseudomonas, Pseudomonas, Pseudomonas, Pseudomonas, Pseudomonas, Pseudomonas, Pseudomonas, Pseudomonas, Pseudomonas, Pseudomonas, Pseudomonas, Pseudomonas, Pseudomonas, Pseudomonas, Pseudomonas, Pseudomonas. P. cubensis, P. cubensis. A species of the genus Pseudoperonospora (Pseudoperonospora spp.) Including P. humuli, Pseudopeziza tracheipila, P. Holdei, P. hordei, P. Recondita, P. recondita, P. P. triiformis, P. triiformis, P. A species of the genus Puccinia (Puccinia spp.) Including Triticina, a species of the genus Pyrenopeziza (Pyrenopeziza spp), a species of the genus Pyrenopeziza (Pyrenopeziza spp), a species of the genus Pyrenopeziza (Pyrenopeziza spp) (Pyricularia spp.), P.I. Rhizoctonia spp, a Ramularia spp, a Rhizoctonia spp, a Rhizoctonia spp, a Rhizoctonia sp, a Rhizoctonia sp, a Rhizoctonia spp, a Rhizoctonia spp, a Rhizoctonia spp, a Rhizoctonia spp, a Rhizoctonia spp, a Rhizoctonia spp, a Rhizoctonia sp. , A species of the genus Rhizoctonia (Rhizoctonia spp), S. S. apiospermum and S. apiospermum. A species of the genus Sedosporium (Scedosporium spp.), Which includes prolifecans, Schizothirium pomi,
A species of the genus Sclerotia (Sclerotia spp), a species of the genus Sclerotium (Sclerotium spp), S. S. nodolum, S. A species of the genus Septoria (Septoria spp), including S. tritici, a species of Sphaerotheca macularis, a species of Sphaerotheca fusca (a species of Sphaerotheca friginea, a species of Sphaerotheca friginea). (Sporothorix spp), Stagonospora nodolum, a species of the genus Stemphyllium (Stemphylyum spp.), Stereum hilsutum, Tanatehols kucumeris, Thanathephors Kora (Thielaviopsis basicola), a species of the genus Tilletia (Tilletia spp), T.I. T. harzianum, T. harzianum. Pseudokoningii, T. pseudokoningii, T. pseudokoningii. A species of the genus Trichoderma (Trichoderma spp.), Including T. viride,
Trichophyton spp, Cyphula spp, Uncinula necator, Urocystis spp, Ustilago spp, V. typhophyton spp, Ustilago spp, Ustilago spp A species of the genus Venturia (Venturia spp.), A species of the genus Verticillium (Verticillium spp) and a species of the genus Xanthomonas (Xanthomonas spp), including V. inaequalis.

In particular, using the compound of formula (I) containing these and the bactericidal / fungal composition, Basidiomycete, Ascomycete, Oomycete and / or incomplete fungi, It can control plant diseases caused by a wide range of fungal phytopathogens in Brasocladiomycete, Chrytidiomycete, Glomeromycete and / or Mucoromycete.

Examples of these pathogens include:
Oomycete, which includes: Phytophthora capsici, Phytophthora phytophthora infestans, Phytophthora sojae, Phytophthora Phytophthora Phytophthora Phytophthora Phytophthora Phytophthora Phytophthora Phytophthora Phytophthora Phytophthora Phytophthora (Phytophthora cytophthora), Phytophthora cytophthora, Phytophthora cytophthora and Phytophthora phytophthora Phytophthora phytophthora phytophthora phytophthora phytophthora phytophthora phytophthora phytophthora phytophthora Phytophthora Phytophthora, Phytophthora, Phytophthora, Phytophthora, Phytophthora, Phytophthora, Phytophthora, Phytophthora, Phytophthora, Phytophthora, Phytophthora, Phytophthora, Phytophthora. Phytophthora destoructor, Phytophthora parasicica, Phytophthora phytophthora, Phytophthora phytophthora, Phytophthora phytophthora Phytophthora Phytophthora macrosora, Phytophthora macrosora, Phytophthora macrosora, Phytophthora phytophthora, Phytophthora, Phytophthora, Phytophthora, Phytophthora, Phytophthora, Phytophthora, Phytophthora, Phytophthora, Phytophthora Aphanomyces cochlioides), Labyrinthula zosterae, Peronosclerospora sorghi and Others such as Sclerospora glamicola.

Ascomycetes, for example, Stemphylium solani, Stagonospora tainanensis, Spirocaea oleaginea (Spirocaea oleasia). Turcica), Pyrenophora lycoperisici, Pleospora herbalum, Pyrenophora herbarum, Phoma destructiva, Phaeosfaeria helpoidea Phaeocryptocus gaeumannii, Ophiosphaerella glaminicola, Ophiobolus graminis, Leptosphaeria helmaeris henma renspourema rens Helminthosporium tricicirepentis, Setosphaeria turcica, Drechslera glycines, Didymera brionie colynecomia Corynespora cassicola, Cochliobolus sativus, Bipolaris cactivora, Pyrenophora trinopsis, Pyrenophora trino, Pyrenophora trino, Pyrenophora trino, Pyrenophora trino, Pyrenophora trino, Pyrenophora trino, Pyrenophora trino, ), Alternaria alternata, Alternaria brassicola, Alternaria sora Cladosporales such as D. (Alternaria solani) and Alternaria tomatofila; Septria tritici, Septria nodolm (Septoria nocelline), Septria nocellium Cercospora arachidicola, Cercospora sojina, Cercospora zeae-maydis, Cercospora zeae-maydis, Cercosporera capsero celcosporella celcosporella celcosporella Capnodiales, such as Cladosporium carpofilum, Cladosporium effusum, Passalora fulva, Cladosporium oxysporium, Cladosporium oxysporium, Cladosporium oxysporium, Cladosporium Mu (Dothystroma septosporum), Isariopsis cladospora, Mycosphaerella fijiensis, Mycosphaerella fijiensis, Mycosphaerella gymoseptoria tricosphaerella gymoseptoria trichophylla Tachicola (Phaeoisariopsis bataticola), Pseudocercospora vitis, Pseudocercosporella herpotricoids (Pseudocercosporella herpotrichoides), Lambaria beticola (Lambaria beticola), Lambaria beticola (Pseudocercosporella herpotorichoides) Mrs. Graminis (Gaeumannomyces graminis), Magnaporte gris ea), Magnaporthes such as Pyricularia oryzae; Anisogramma anomala, Apiognomonia elabunda, Apiognomonia elabunda (Apiognomonia) Diaporthe phaseolorum, Discula destructiva, Gnomonia fructicola, Greeneria ubicola, Greenelia ubicola, Greeneria ubicola, Greeneria ubicola, Greeneria ubicola, Viticola), Sirococcus clavignenti-juglandacearum, Tubakia dryina, a species of the genus Dicarpella spp. ), Diaportes such as Valsa ceratosperma; as well as Actinothyrium graminis, Aspergillus spilus spilus spilus spilus spilus spilus spilus spilus spilus spilus spilus spilus spilus spilus spilus flavus aspergillus flavus. ), Aspergillus nidulans, Aspergillus caricae, Blumeriella jaapii, a species of the genus Candida (Candida spp.), Capnodium spp. A species of the genus Cephaloascus (Cefaloascus spp.), A species of Cephalosporium gramineum, a species of Ceratocystis paradoxa, a species of the genus Chitomium (Chaetomium sp.), A species of Aspergillus sp. pseudoalbidus), a species of the genus Aspergillus (Coccidioides spp.), Cylindrosporium padi, Diprocarpon malae, Drepanope dizacampestris (Drepanopedi zacampes pes)
Elsinoe ampelina, Epicoccum nigrum, a species of the genus Epidermophyton (Epidermophyton spp.), Euchipa lata, Geotricillium candism (Geotricum candism) Caused by other things such as (Gibellina cerealis), Gloeocercospora sorghi, Gloeodes pomigena, Gloeosporium perenans Diseases, blast disease or blight and / or spoilage; Gloeotinia temculenta, Griphospaeria corticola, Kabatiella limi, leptographi, leptographi , Leptosphaerulinia classiasca, Lophodermium sediciosum, Marssonina graminicola, Marssonina graminicola, Komugi red mold fungus Fructicola), Monographella albessens, Monosporascus cannonbolus, a species of the genus Naemacyclus (Naemacyclus spp.), Offiostomano spo-mio-paras (Penicillium expansum), Penicillium expansum, Pestalocia rhododendri, Petriellidium spp., Petriellidium spp., Petriellidium spp., Petriellidium spp. Phyalophora gregata, Phyllachora pomigena, Phymatotrichum omnivora, Physarophora psibula psibita, Physalospora pysalospora Polysytalum pustulans, Pseudopeziza medicaginis, Pyrenopeziza brassicae, Ramrispora sporinga squirrel squirrel squirrels, squirrels, squirrels, squirrels, squirrels, squirrels, squirrels, squirrels, squirrels, squirrels, squirrels, squirrels, squirrels, squirrels. Rymchosporium secalis, Rice leaf rot rotase (Sacrocladium oryzae), a species of the genus Skedosporium spp. ), Schizothyrium pomi, Sclerotinia sclerotiorum, Sclerotinia minor; Sclerotiium spyl, a species of the genus Sclerotiium sp. Seimatosporium mariae, Lepteupa cupressi, Septocyta ruborum, Sphaceloma perse (Sphaceloma perse), Sphaceloma perseide, Sphaceloma persea (Stigmina palmivora), Tapeshiayarunde (Tapesia yallundae), Tafurinaburata (Taphrina bullata), Chi shrimp Opsys Basi kola (Thielviopsis basicola), Trichoderma concept rear guru lipped Gena (Trichoseptoria fructigena), Gigot Fiala Jami forsythensis (Zygophiala jamaicensis); e.g. Bull Melia Gras Minis (Blumeria graminis), Erysiphaceae polygoni, Uncinula necator, Sphaerotheca fuligena, Sphaerotheca fuligena, Apple powdery mildew (Podo) Podos powdery mildew, powdery mildew, powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew powdery mildew Powdery mildew diseases such as those caused by Erysiphaceae such as guttata) and Oidium arachidis; eg, powdery mildew aromatica (Dotiorella aromatica), Diprodia seriata, Guignardia bidwellii, Botrytis cinerea, Botritiis cineria, Botriotiis cinerea, Botriotiis cinerea Fusarium amygdali, Lasiodiplodia theobromae, Macroforma theicola, Macrofomina theicola, Macrofomina faseolina (Macrophomina faseolina) Molds such as those caused by the order Fusarium (Fusarium); for example, Colletotricum gloeosporioides, Colletotricum lagenarium, Colletotricum lagenarium, Colletotricum lagenarium, etc. Fusarium, such as those caused by the genus Glommeralales, such as Glomerella cingulata and Colletotricum graminicola; and, for example, accremonium stricum, Acrem (Clavipeps purpurea), Fusarium culmorum, Fusarium graminearum, Fusarium virguliforme, Fusarium oxysporum, Fusarium oxysporum, Fusarium oxysporum. , Fusarium oxysporum f. sp. cubense), Gerlacia nivale, Gibberella fujikuroi, Gibberella zeae, Gibberella zeae, a species of the genus Gliocladia, Gibberella zeae, Gliocladium sp. Hypocreales such as Nectria ramulariae, Trichoderma viride, Trichothecium roseum and Hypocreales caused by Hypocreales such as Hypocreales or Hypocreales. Trichoderma virideis.

For example, Rust such as Ustiraginoidea virens, Ustirago nuda, Ustirago tritici, and Ustirago zeae caused by basidiomycetes such as Ustirago zeae Basidiomycete, such as Celotelium fici, Chrysomyxa arctostaphyli, Choreosporium ipomoea (Coleosporium ipomia), basidiomycete Puccinia arachidis, Puccinia cabacata, Puccinia graminis, Puccinia recondita, Puccinia recondita, Puccinia recondita, Puccinia recondita, Puccinia sorghi Rust such as Miss (Puccinia striiformis f.sp.Hordei), Puccinia striiformis f.sp.Secalis, Pucciniastrium coryli (Cronartium rivicola), Jimnosporangium juniperi-viginianae, Melampsora medusae, Facopsora puccinia (Puccinia) Puccinia (Puccinia), Puccinia (Puccinia) Rusts such as Physopela ampelosides, Transscheria discolor and Uromyces viciae-fabae Rust fungi, such as those caused by the order Rust; as well as a species of the genus Cryptococcus (Cryptococcus spp. ), Exobasideium vexans, Marasmiellus inorderma, a species of the genus Mycena (Mycena spp.), Sphacellotecareliiana, Urosistis agropyri, Itersonilia perplexans, Corticium invisum, Laetisaria fushihoris, Laetisaria tyacior Rhizoctonia solani, Rhizoctonia sulani, Tilletonia culmeris, Entyroma dahliae, Entylomera microspora (Entyloma la tyaria tyaria tyaria microssa), Neo Other rot and diseases such as those caused by.

Blastocladiomycetes such as Physodermama mydis.

Choanephora cubitalum; a species of the genus Mucor (Mucor spp.); Mucoromycetes such as Rhizopus arrhizus.
And diseases caused by other species and genera closely related to those listed above.

In addition to its bactericidal and antifungal activity, the compounds and compositions containing them are also Erwinia amylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonas campestris, Pseudomonas campestris. It can have activity against bacteria and other related species, such as frogs (Pseudomonas syringae), Strptomyces scabies, and certain protozoa.

Within the scope of the invention, the target crops and / or useful plants to be protected are typically liquid fruit plants such as, for example, blackberries, blueberries, cranberries, peanuts and strawberries; such as bean, corn. , Milles such as millet, peanut, rice, rye, sorghum peanut and wheat; fiber plants such as cotton, flax, asa, jute and sisal; eg sugar and feed beet, coffee, hops, mustard, abrana (canola) ), Poppies, sugar cane, sunflowers, cha and tobacco; fruit trees such as apples, apricots, avocados, bananas, cherries, citrus fruits, nectarins, peaches, pears and peaches; eg Bermudagrass, strawberry tuna, bentgrass, centipedegrass , Ushinokegusa, ryegrass, American shiva and noshiba; herbs such as basil, rurigisa, chives, coriander, lavender, lavage, mint, oregano, parsley, rosemary, sage and thyme; for example, bean, lens bean, peanut and soybean, Bean plants such as common beans; nuts such as almonds, cashews, peanuts, hazelnuts, peanuts, pecans, pistachios and walnuts; palms such as abra palms; ornamental plants such as flowers, shrubs and trees; such as cacao, coconut, olive and rubber. Other trees; vegetables such as asparagus, eggplant, broccoli, cabbage, carrots, cucumbers, garlic, lettuce, pepo pumpkins, melons, okra, onions, peppers, potatoes, pumpkins, daisou, spinach and tomatoes; and vines such as grapes. Includes perennial and annual crops such as plants.

Useful plants and / or target crops according to the present invention are, for example, insect-resistant (eg, Bt. And VIP varieties) and disease-resistant, herbicide-resistant (trade names RoundupReady® and LibertyLink®). Includes conventional varieties such as commercially available (eg, glyphosate- and glufosinate-resistant corn varieties) and nematode resistant varieties, as well as genetically enhanced or genetically engineered varieties. As an example, preferably genetically fortified or genetically engineered varieties include Stoneville 5599BR cotton and Stoneville 4892BR cotton varieties.

The terms "useful plant" and / or "target crop" are used by conventional mating or genetic manipulation methods to provide herbicides such as bromoxinyl, or a class of herbicides (eg, HPPD inhibitors, ALS inhibitors, etc.). For example, primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovir-shikimate-3-phosphate-synthase) inhibitor, GS (glutamine synthetase) inhibitor or PPO (protoporphyrinogen-oxidase). It should also be understood to include useful plants that have been conduced to resistance to) inhibitors, etc.). An example of a crop in which conventional mating methods (mutagenesis) have resulted in resistance to imidazolinone, such as imazamox, is Clearfield® Summer Rapeseed (Canola). Examples of crops that have been genetically engineered to resist herbicides or certain classes of herbicides are commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®. Glyphosate- and glufosinate-tolerant maize varieties can be mentioned.

The terms "useful plants" and / or "target crops" should be understood to include those that are spontaneous or that have been endowed with resistance to harmful insects. This includes plants transformed by using recombinant DNA technology, eg, to have the ability to synthesize one or more selectively acting toxins, such as those known to be derived from toxin-producing bacteria. Examples of toxins that can be expressed include δ-endotoxin, vegetative insecticidal protein (Vip), nematode symbiotic bacterial insecticidal protein, as well as scorpions, arachnids, and large wasps. And toxins produced by fungi. An example of a crop that has been denatured to express Bacillus thuringiensis toxin is Bt maize KnockOut® (Syngenta Seeds). An example of a crop that contains two or more genes encoding insecticidal resistance and therefore expresses two or more toxins is VipCot® (Syngenta Seeds). The crop or its seed material can also be resistant to multiple pests (so-called superposed transgenic events when formed by genetic modification). For example, plants can be herbicide-tolerant and at the same time capable of expressing insecticidal proteins, such as Herculex I® (Dow AgroSciences, Pioneer Hi-Bred International).

The terms "useful plants" and / or "target crops" are selective actions such as, for example, so-called "pathogenesis-related proteins" (PRP, see, eg, European Patent Application Publication No. 0392225). It should be understood that it also includes useful plants that have been transformed using recombinant DNA technology to be able to synthesize anti-pathogenic substances having. Examples of such anti-pathogenic substances and transformed plants capable of synthesizing such anti-pathogenic substances are, for example, European Patent Application Publication No. 0392225, International Publication No. 95/33818. And European Patent Application Publication No. 0 353 191. Methods for producing such transformed plants are generally known to those skilled in the art and are described, for example, in the above publication.

Toxins that can be expressed by the transformed plant include, for example, an insecticidal protein derived from Bacillus cereus or Bacillus popillia; or, for example, Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A. , Cry3Bb1 or Cry9C and other Bacillus thuringiensis-derived insecticidal proteins such as δ-endotoxin, or nutritional insecticidal proteins (Vip) such as Vip1, Vip2, Vip3 or Vip3A; Photohabdus luminesces, Xenorhabdus nematophilus, etc., for example, a species of Photolabdus spp. , Spider toxins, toxins produced by animals such as large wasp toxins and other insect-specific neurotoxins; toxins produced by fungi such as Streptomycete toxin, pea melectin, omugilectin or matsuyukisou Plant lectins such as lectin; aglutinin; proteinase inhibitors such as trypsin inhibitors, serine proteolytic enzyme inhibitors, patatin, cystatin, papain inhibitors; ribosomes such as lysine, corn-RIP, abrin, rufin, saporin or briozin Activated protein (RIP); 3-hydroxysteroid xidase, exdisteroid-UDP-glycosyl-transferase, cholesterol oxidase, ecdison inhibitor, steroid metabolizing enzymes such as HMG-COA-reductase, ion channels such as sodium or calcium blockers Included are blockers, larvae hormone esterases, diuretic hormone receptors, stillben synthase, bibenzyl synthase, chitinase and glucanase.

Further, in the context of the present invention, delta-endotoxins such as Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins such as Vip1, Vip2, Vip3 or Vip3A (Vip). It should be understood that is also a hybrid toxin, a truncated toxin and a modified toxin in particular. Hybrid toxins are recombinantly produced by a new combination of different domains of these proteins (see, eg, WO 02/15701). Cleaved toxins such as cleaved Cry1Ab are known. In the case of modified toxins, one or more amino acids of the natural toxins are replaced. In such amino acid substitutions, preferably a non-naturally occurring proteolytic enzyme recognition sequence is inserted into the toxin, for example, in the case of Cry3A055, the cathepsin-G-recognition sequence is inserted into the Cry3A toxin (International Publication No. 03). / 018810).

Further examples of such toxins, or transformed plants capable of synthesizing such toxins, are, for example, European Patent Application Publication No. A-0 374 753, WO 93/07278, WO 93. It is disclosed in European Patent Application Publication No. 95/34656, European Patent Application Publication No. A-0 427 529, European Patent Application Publication No. A-451 878 and International Publication No. 03/052073.

The process of preparing such transformed plants is generally known to those of skill in the art and is described, for example, in the publications described above. CryI-type deoxyribonucleic acid and its preparation are described, for example, in International Publication No. 95/34656, European Patent Application Publication No. A-0 367 474, European Patent Application Publication No. A-0 401 979 and International Publication. It is known from No. 90/13651.

Toxins contained in transformed plants confer resistance on harmful insects on the plants. Such insects can belong to any of the insect classifications, but are commonly found in Coleoptera (Coleoptera), Diptera (Diptera) and Butterflies (Lepidoptera).

Transformed plants that contain one or more genes that encode insecticidal resistance and express one or more toxins are known, some of which are commercially available. Examples of such plants are: YieldGard® (Cry1Ab toxin-expressing corn varieties); YieldGardRootworm® (Cry3Bb1 toxin-expressing corn varieties); YieldGard Plus® (Cry1Ab and Cry3Bb1 toxin). Starlink® (Cry9C toxin-expressing corn varieties); Herculex I® (Cry1Fa2 toxin and the enzyme phosphinotricin N-acetyltransferase (PAT) expressing the herbicide gluhosinate) Corn varieties that have achieved resistance to ammonium); NuCOTN 33B® (cotton varieties expressing Cry1Ac toxin); Bollgard I® (cotton varieties expressing Cry1Ac toxin); Bollgard II® (Cotton varieties expressing Cry1Ac and Cry2Ab toxin); VipCot® (Cotton varieties expressing Vip3A and Cry1Ab toxin); NewLeaf® (Potato varieties expressing Cry3A toxin); NatureGard®,. Agrisure® GT Advantage (GA21 glyphosate-resistant trait), Agrisure® CB Advantage (Bt11 cone perforating pest (CB) trait) and Protecta®.

Further examples of such transformed crops are:
1. 1. Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France Bt11 corn, registration number C / FR / 96/05/10. Genetically engineered maize that has been conferred resistance to corn borer (European borer (Ostrinia nubilalis) and Sesamia nonagrioides) by transgenic expression of truncated Cry1Ab toxin. Bt11 maize also transgenically expresses the enzyme PAT to achieve resistance to the herbicide glufosinate ammonium.

2. 2. Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France Bt176 corn, registration number C / FR / 96/05/10. Genetically engineered maize that has been conferred resistance to corn borer (European borer (Ostrinia nubilalis) and Sesamia nonagrioides) by transgenic expression of Cry1Ab toxin. Bt176 maize also transgenically expresses the enzyme PAT to achieve resistance to the herbicide glufosinate ammonium.

3. 3. Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France MIR604 corn, registration number C / FR / 96/05/10. Maize conferred insect resistance by transgenic expression of modified Cry3A toxin. This toxin is Cry3A055 modified by the insertion of a cathepsin-G-proteolytic enzyme recognition sequence. The preparation of such transformed maize plants is described in WO 03/018810.

4. Monsanto Europe S.A. A. 270-272 Avenue de Tervueren, B-1150 Brussels, Belgium MON863 corn, registration number C / DE / 02/9. MON863 expresses Cry3Bb1 toxin and has resistance to certain Coleoptera insects.

5. Monsanto Europe S.A. A. 270-272 Avenue de Tervueren, B-1150 Brussels, Belgium IPC531 cotton, registration number C / ES / 96/02.

6. Pioneer Oversea Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium 1507 corn, registration number C / NL / 00/10. A corn genetically engineered for the expression of the protein Cry1F, which achieves resistance to certain lepidopteran insects, and the PAT protein, which achieves resistance to the herbicide glufosinate ammonium.

7. Monsanto Europe S.A. A. 270-272 Avenue de Tervueren, B-1150 Brussels, Belgium NK603 x MON810 corn, registration number C / GB / 02 / M3 / 03. It consists of a conventional hybrid corn variety by crossing the genetically engineered varieties NK603 and MON810. NK603 × MON810 maize transgenically expresses the protein CP4 EPSPS obtained from the strain CP4 of the genus Agrobacterium (Agrobacterium sp.), Which makes it resistant to the herbicide Roundup® (containing glyphosate). Cry1Ab toxins conferred and obtained from Bacillus thuringiensis subsp. Kurstaki are transgenically expressed, which results in resistance to certain corns, including Agrobacterium.

As used herein, the term "habitat" means the field in which the plant is growing, or the field in which the seeds of the cultivated plant are sown, or the seeds are sown in the soil. It means a field. This includes soil, seeds and seedlings, as well as established vegetation.

The term "plant" refers to all physical parts of a plant, including seeds, seedlings, seedlings, roots, tubers, stems, stalks, herds and fruits.

The term "plant reproductive material" is understood to refer to the reproductive part of a plant, such as seeds, which can be used for its reproduction, and to nutrients such as cuttings or tubers, such as potatoes. For example, seeds (in a strict sense), roots, fruits, tubers, bulbs, rhizomes and plant parts can be mentioned. Also included are germinated plants and young shoots that will be transplanted after germination or after emergence from the soil. These young shoots may be protected by complete or partial treatment by immersion prior to transplantation. Preferably, the "plant breeding material" is understood to represent a seed.

Pest control agents referred to herein using trivial names include, for example, "The Pesticide Manual", 15th Ed. , British Crop Protection Council 2009.

The compound of formula (I) can be used in its original form or, preferably with an adjunct that is conveniently employed in the art of formulation. For this purpose they are, in a known manner, emulsifying concentrates, coating pastes, direct injectable or dilute solutions or suspensions, diluted emulsions, wettable powders, soluble powders, powders, granules, And, for example, it can be easily blended into a capsule in a polymer substance. As with the type of composition, application methods such as spraying, spraying, dusting, spraying, coating or pouring are selected depending on the intended purpose and the circumstances at the time. Compositions are also stabilizers, defoamers, viscosity modifiers, binders or adhesives, and additional aids such as fertilizers, trace element sources, or other formulations to obtain special effects. May be contained.

Suitable carriers and auxiliaries used in agriculture, for example, can be solid or liquid and are useful substances in compounding techniques, such as natural or regenerated minerals, solvents, dispersants, wetting agents, adhesives. , Thickener, binder or fertilizer. Such carriers are described, for example, in WO 97/3389.

Suspension concentrates are aqueous formulations in which fine solid particles of the active compound are suspended. Such formulations may include anti-settling agents and dispersants, as well as wetting agents and antifoaming agents and crystal growth inhibitors to enhance activity. In use, these concentrates are diluted in water and usually sprayed onto the area to be treated. The amount of active ingredient can be in the range of 0.5% to 95% of the concentrate.

Wettable powders are in the form of fine particles that are easily dispersed in water or other liquid carriers. These particles contain the active ingredient retained in the solid matrix. Typical solid matrices include fuller clay, kaolin clay, silica and other moisture-sensitive organic or inorganic solids. Wettable powders usually contain 5% to 95% of the active ingredient and a small amount of wetting agent, dispersant or emulsifier.

The emulsifying concentrate is a homogeneous liquid composition that is dispersible in water or other liquids and may consist only of the active compound and a liquid or solid emulsifier, or xylene, a high boiling point aroma. It may contain liquid carriers such as group naphtha, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquids and are usually sprayed onto the area to be treated. The amount of active ingredient can be in the range of 0.5% to 95% of the concentrate.

Granular formulations contain both extruded and relatively coarse particles and are usually applied undiluted to areas where treatment is required. Typical carriers for granular formulations are sand, fuller soil, attapargite clay, bentonite clay, montmorillonite clay, vermiculite, pearlite, calcium sulphate, bricks, which can absorb or coat the active compound. , Palletite, leaf wax, kaolin, dolomite, roasted gypsum, wood flour, crushed corn cob, crushed peanut shell, sugar, sodium chloride, sodium sulfate, sodium silicate, sodium borate, magnesia, mica, Examples include iron oxide, zinc oxide, titanium oxide, antimony oxide, glacial stone, gypsum, diatomaceous earth, calcium sulphate and other organic or inorganic materials. Granular formulations usually contain 5% to 25% of the active ingredient, which is a surface active agent such as high boiling aromatic naphtha, kerosene and other petroleum fractions, or vegetable oils; and / or dextrin, glue. Alternatively, it may contain a spreading agent such as a synthetic resin.

The powder is an easily fluid mixture of the active ingredient and fine solids such as talc, clay, powder and other organic and inorganic solids that act as dispersants and carriers.

Microcapsules are typically droplets or granules of active ingredient encapsulated in an inert porous shell capable of releasing the encapsulated material to the surroundings at a controlled rate. Encapsulated droplets are typically 1 to 50 microns in diameter. The encapsulated liquid typically constitutes 50-95% of the weight of the capsule and may contain a solvent in addition to the active compound. Encapsulated granules are generally porous granules with a porous membrane that seals the pore openings of the granules and retains the active species in liquid form within the pores of the granules. Granules typically have a diameter in the range of 1 millimeter to 1 centimeter, preferably 1-2 millimeters. Granules are formed by extrusion, agglomerates or prills, or are natural. Examples of such materials are vermiculite, calcined clay, kaolin, attapulsite clay, sawdust and granular carbon. Shell or membrane materials include natural and synthetic rubbers, cellulose-based materials, styrene-butadiene copolymers, polyacrylonitrile, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch zandates.

Other useful formulations for agrochemical applications include simple solutions of the active ingredient in solvents that achieve complete dissolution at the desired concentration, such as acetone, alkylated naphthalene, xylene and other organic solvents. .. A pressure sprayer can also be used in which the active ingredient is sprayed into finely separated forms as the low boiling point dispersant solvent carrier evaporates.

Suitable agricultural aids and carriers useful in formulating the compositions of the invention of the above formulation type are well known to those of skill in the art.

Available liquid carriers include, for example, water, toluene, xylene, petroleum naphtha oil, crop oil, acetone, methyl ethyl ketone, cyclohexanone, anhydrous acetic acid, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol. , Alkyl acetate, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol aviate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N, N-dimethylformamide, dimethylsulfoxide, 1, , 4-Dioxane, Dipropylene Glycol, Dipropylene Glycolmethyl Ether, Dipropylene Glycol Dibenzoate, Diproxitol, Alkylpyrrolidinone, Ethyl acetate, 2-Ethylhexanol, Ethylene Carbonate, 1,1,1-Trichloroethane, 2-Heptanone , Α pinen, d-lymonen, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, γ-butyrolactone, glycerol, glycerol diacetic acid, glycerol monoacetic acid, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane , Isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityloxide, methoxy-propanol, methylisoamyl ketone, methylisobutylketone, methyl laurate, methyloctanoate, methyl oleate, methylene chloride, m-xylene, n-hexane, n-octylamine, cutadecanoic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol (PEG400), propionic acid, propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene, Triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, methanol, ethanol, isopropanol, and amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol High molecular weight alcohol such as, ethylene glycol, propi Lenglycol, glycerin and N-methyl-2-pyrrolidinone can be mentioned. Water is the carrier of choice for diluting concentrates.

Suitable solid carriers include, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapargit clay, key slugger, choke, diatomaceous earth, lime, calcium carbonate, bentonite clay, fuller soil, cottonseed shell, flour, soybean. Examples include flour, pumice, wood flour, walnut shell flour and lignin.

A wide range of surfactants are advantageously utilized in both liquid and solid compositions, especially those designed to be diluted with carriers prior to application. These surfactants, when used, usually contain 0.1% to 15% by weight of a formulation. They can be anionic, cationic, nonionic or polymeric in nature and can be used as emulsifiers, wetting agents, suspending agents or for other purposes. Typical surfactants include alkyl sulphates such as diethanolammonium lauryl sulfate; alkylaryl sulfonates such as calcium dodecylbenzenesulfonate; nonylphenol-C. sub. Alkylphenol-alkylene oxide addition products such as 18 ethoxylates; tridecyl alcohol-C. sub. 16 Alcohol-alkylene oxide addition products such as ethoxylate; soaps such as sodium stearate; alkylnaphthalene sulfonates such as sodium dibutylnaphthalene sulfonate; dialkyl esters of sulfosuccinates such as di (2-ethylhexyl) sodium sulfosuccinate Sorbitol esters such as sorbitol oleate; quaternary amines such as lauryltrimethylammonium chloride; polyethylene glycol esters of fatty acids such as polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono and dialkyl phosphate esters Can be mentioned.

Other auxiliaries commonly used in agricultural compositions include crystallization inhibitors, viscosity modifiers, suspending agents, spray granule modifiers, pigments, antioxidants, foaming agents, defoamers, shading agents, etc. Solubilizers, defoamers, metal ion sequestering agents, neutralizers and buffers, corrosion inhibitors, dyes, odorants, spreading agents, penetrating aids, trace elements, easing agents, lubricants and fixing agents. Be done.

In addition, other killing active ingredients or compositions may be combined with the compositions of the invention, used in the methods of the invention, and applied simultaneously or sequentially with the compositions of the invention. When applied at the same time, these additional active ingredients may be formulated with the compositions of the invention or, for example, mixed together in a spray tank. These additional killing active ingredients can be fungicides / fungicides, herbicides, insecticides, fungicides, acaricides, nematodes and / or plant growth regulators.

In addition, the compositions of the present invention can also be applied with one or more systemic acquired resistance inducers (“SAR” inducers). SAR inducers are known and are described, for example, in US Pat. No. 6,919,298, including salicylate and the commercially available SAR inducer, acibenzolar-S-methyl.

The compounds of formula (I) are usually used in the form of compositions and can be applied to crop areas or plants to be treated at the same time as or sequentially with additional compounds. These additional compounds can be, for example, fertilizers or trace element donors, or other preparations that affect plant growth. These can also be selective or non-selective herbicides, as well as pesticides, fungicides / fungicides, fungicides, nematodes, mollusk repellents, or Mixtures of several of these preparations can be, if desired, mixtures with additional carriers, surfactants or application facilitators commonly used in the field of formulations.

The compound of formula (I) can be used in the form of a (bactericidal / mold-killing) composition for controlling or protecting phytopathogenic microorganisms, which comprises at least one compound of formula (I) as an active ingredient. Alternatively, it may be used in the form of at least one preferred individual compound as defined above in free form or agrochemically usable salt form and at least one of the above-mentioned auxiliary agents.

The present invention therefore provides compositions, preferably bactericidal and fungicidal compositions, comprising at least one compound of formula (I), an agronomically acceptable carrier, and optionally an adjunct. Agriculturally acceptable carriers are, for example, suitable carriers for agricultural applications. Agricultural carriers are well known in the technical field. Preferably, the composition may contain, in addition to the compound of formula (I), at least one or more pest control active compounds, such as an additional bactericidal and fungicidal active ingredient.

The compound of formula (I) may be the only active ingredient in the composition and, where appropriate, a pest control agent, a bactericidal / fungicidal agent, a synergist, a herbicide or a plant growth regulator, etc. May be mixed with one or more additional active ingredients of. Additional active ingredients can, in some cases, result in unexpected synergistic activity.

Examples of suitable additional active ingredients include: 1,2,4-thiasiazole, 2,6-dinitroaniline, acylalanine, aliphatic nitrogen compounds, amidins, aminopyrimidinol, anilides, anilinopyrimidines, anthraquinones. , Antibiotics, arylphenylketone, benzamide, benzenesulfonamide, benzoimidazole, benzothiazole, benzothiodiazole, benzothiophene, benzoylpyridine, benzothiazole, benzylcarbamate, butylamine, carboxamide, carboxamide, carpropamide , Chloronitrile, silicate amide, copper-containing compound, cyanoacetamide oxime, cyanoacrylate, cyanoimidazole, cyanomethylene thiazolidine, dicarbonitrile, dicarboxamide, dicarboxymid, dimethylsulfamate, dinitrophenol carbonate, dinitrophenyl ( dinitrophenysl), dinitrophenyl crotonate, diphenyl phosphate, dithino compound, dithiocarbamate, dithioether, dithiolane, ethylaminothiazole carboxamide, ethylphosphonate, furan carboxamide, glucopyranosyl, glucopyranoxyl, glutaronitrile, guanidine, Herbicides / plant growth regulators, hexopyranosyl antibiotics, hydroxy (2-amino) pyrimidine, hydroxyanilide, hydroxyisoxazole, imidazole, imidazolinone, pesticides / plant growth regulators, isobenzofuranone, isooxazolidinylpyridine , Isooxazoline, Maleimide, Mandelic acid amide, Mectin derivative, Morpholine, Norphorin, n-phenylcarbamate, Organic tin compound, Oxatiincarboxamide, Oxazole, Oxazolidinedione, Phenol, Phenoxyquinoline, Phenylacetamide, Phenylamide, Phenylbenzamide, Phenyl Oxoethylthiophenamide, phenylpyrrole, phenylurea, phosphorothiolate, phosphite, phthalamide acid, phthalimide, picolinamide, piperazine, piperidine, plant extract, polyoxine, propionamide, phthalimide, pyrazole-4-carboxamide , Pyrazolinone, pyridadinone, pyridine, pyridineka Luvoxamide, pyridinyl ethylbenzamide, pyrimdinamine, pyrimidine, pyrimidineamine, pyrimidine hydrazone, pyrrolidine, pyrrolquinolinone, quinazolinone, quinoline, quinoline derivative, quinoline-7-carboxylic acid, quinoxalin, spiroketamine. Strobiylline, sulfamoyltriazole, sulfamide, tetrazolyloxime, thiazidein, thiazylcarboxamide, thiazole carboxamide, thiocianate, thiophenecarboxamide, toluamide, triazine, triazobenchazole, triazole, triazolethion, triazolopyrimidylamine , Valinamide carbamate, ammonium methylphosphonate, arsenic-containing compound, benzoimidazolyl carbamate, carbonitrile, carboxanilide, carboxymidamide, carboxylic acid phenylamide, diphenylpyridine, fluanilide, hydrazine carboxamide, imidazoline acetate, isophthalate, isoxazolone. Salts, organic mercury compounds, organic phosphates, oxazolidinedione, pentylsulfonylbenzene, phenylbenzamide, phosphonothionate, phosphorothioate, pyridylcarboxamide, pyridylfurfuryl ether, pyridylmethyl ether, SDHI, thiadiadinanthion, thiazolidine.

A further aspect of the present invention is a human being of a plant, eg, a useful plant, eg, a crop plant, a plant propagation material thereof, eg, a seed, a harvested crop, eg, a harvested food crop, or a non-biological material. With respect to a method of controlling or preventing ectoparalysis by phytopathogenic or spoilage microorganisms or organisms that are potentially harmful to, in particular fungal organisms, this method is defined in the compounds of formula (I) or above. It comprises applying the preferred individual compound as an active ingredient to any part of a plant, plant part or habitat thereof, plant propagation material thereof, or non-biological material.

Control or prevention is the reduction of ectoparasitism by insects, or especially by phytopathogenic organisms such as fungal organisms or by putrefactive microorganisms or organisms that are potentially harmful to humans, to levels where improvement is demonstrated. Means.

In particular, application of an agrochemical composition containing the compound of formula (I) or at least one of the above compounds, which is a preferable method for controlling or preventing ectoparasitism of crop plants by phytopathogenic microorganisms such as fungal organisms or insects. The method including is foliar treatment. The frequency and amount of application will depend on the risk of ectoparasitism by the corresponding pathogen or insect. However, the compounds of formula (I) can also be soiled (penetrated) by irrigating the plant habitat with a liquid formulation, or by applying the compound to the soil, for example in the solid form in granular form (soil application). It is possible to infiltrate the plant from the root through the migration action). In the case of paddy crops, it is possible to apply such granules to paddy fields flooded. The compounds of formula (I) can also be applied (coated) to seeds by impregnating seeds or tubers with a liquid formulation of bactericidal / fungicide, or by coating them with a solid formulation.

Formulations, such as compositions containing a compound of formula (I) and, if desired, a solid or liquid auxiliary agent or monomer that encapsulates the compound of formula (I), are typically in a known manner. Can be prepared by homogeneously mixing and / or grinding the compound with, for example, a solvent, a solid carrier and optionally a bulking agent such as a surface active compound (surfactant).

It should be selected to suit the intended purpose in the epidemic situation and the use of the composition to control the above types of pests, spraying, spraying, dusting, brushing, Another subject of the present invention is a method of applying a composition, which is a method of controlling pests of the above types such as powder coating, diffusion or spraying. A typical concentration ratio is 0.1 to 1000 ppm, preferably 0.1 to 500 ppm of active ingredient. The applied amount per hectare is preferably 1 g to 2000 g of the active ingredient / hectare, more preferably 10 to 1000 g / ha, and most preferably 10 to 600 g / ha. When used as a seed irrigation agent, a convenient dose is 10 mg to 1 g of active substance per 1 kg of seeds.

When the combination of the present invention is used in the treatment of seeds, 0.001 to 50 g of the compound of formula (I) per kg of seeds, preferably 0.01-10 g per kg of seeds, is generally used. Sufficient.

Preferably, the composition containing the compound of formula (I) according to the present invention is applied prophylactically, which means before the outbreak of the disease, or therapeutically, which means after the outbreak of the disease.

The compositions of the present invention are in any conventional form, eg, two-component system, dry seed treatment powder (DS), seed treatment emulsion (ES), seed treatment fluid concentrate (FS), seed treatment. Solution (LS), water-dispersible powder for seed treatment (WS), capsule suspension for seed treatment (CF), gel for seed treatment (GF), emulsion concentrate (EC), suspension concentrate (SC) , Suspo Emulsion (SE), Capsule Suspension (CS), Water Dispersible Granules (WG), Emulsifying Granules (EG), Emulsion, Water in Oil (EO), Emulsion, Oil in Water (EW), Microemulsion (ME), oil dispersion (OD), oil-mixable fluid (OF), oil-mixed liquid (OL), soluble concentrate (SL), ultra-low volume suspension (SU), ultra-low volume Any technically preferred formulation in combination with a liquid (UL), an industrial concentrate (TK), a dispersible concentrate (DC), a wettable powder (WP), or an agriculturally acceptable adjunct. Can be adopted in the form of.

Such compositions, in conventional manners, for example, add the active ingredient to suitable inert formulations (diluents, solvents, fillers, as well as surfactants, killing agents, antifreezes, spreading agents, augmentations. It can be produced by mixing with optionally other ingredients, such as thickeners and compounds that provide the adjuvanting effect. Also, conventional slow-release formulations may be adopted when long-lasting efficacy is intended. In particular, compounds applied in spray form such as water dispersible concentrates (eg EC, SC, DC, OD, SE, EW, EO, etc.), wettable powders and granules include, for example, formaldehyde and naphthalene sulfonates. Surfactants such as condensates with, alkylaryl sulfonates, lignin sulfonates, aliphatic alkyl sulphates, and other compounds that provide wetting and dispersants and adjuvant effects, such as ethoxylated alkyl phenols and ethoxylated fatty alcohols. It may be contained.

The seed powder coating formulation is applied to the seed in a manner known per se and is in a suitable seed powder coating formulation form, for example an aqueous suspension or a dry powder form having good adhesion to the seed, the combination of the present invention. And use a diluent. Such seed powder coating formulations are known in the art. The seed powder coating formulation may contain a single active ingredient or may contain a combination of active ingredients in an encapsulated form, for example as slow-release capsules or microcapsules.

Typically, the formulations are 0.01-90% by weight active agent, 0-20% agriculturally acceptable surfactants, and 10-99.99% solid or liquid inert formulations and supplements. Including agents, the active agent comprises at least a compound of formula (I), together with components (B) and (C) and optionally other active agents, particularly fungicides or preservatives, etc. There is. Concentrated forms of the composition generally contain about 2-80%, preferably about 5-70% by weight of active agent. The application form of the formulation may contain, for example, 0.01 to 20% by weight, preferably 0.01 to 5% by weight of active agent. Commercial products may preferably be formulated as a concentrate, but end users will typically utilize diluted formulations.

It is preferable to formulate a commercially available product as a concentrate, but end users will usually use the formulation diluted.

The following examples illustrate the present invention. Certain compounds of the invention can be distinguished from known compounds by their higher potency at low doses, using the experimental techniques outlined in the Examples, as required, eg, 50 ppm, 12. It can be verified by one of ordinary skill in the art by using smaller doses such as 5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppm or 0.2 ppm.

Throughout the specification, temperature is expressed in degrees Celsius, where "mp" means melting point. LC / MS means liquid chromatography-mass spectrometry.

Formulation Example

The active ingredient can be thoroughly mixed with the auxiliary agent and the mixture can be thoroughly ground in a suitable mill to obtain a wettable powder which can be diluted with water to obtain a suspension of the desired concentration. it can.

The active ingredient is thoroughly mixed with the auxiliary agent and the mixture is thoroughly ground in a suitable mill to give a powder, which can be used directly for seed treatment.

Emulsifying concentrate Active ingredient [Compound of formula (I)] 10%
Octylphenol polyethylene glycol ether 3%
(4-5 mol of ethylene oxide)
Calcium dodecylbenzene sulfonate 3%
Castor oil polyglycol ether (35 mol of ethylene oxide) 4%
Cyclohexanone 30%
Xylene mixture 50%

Emulsions of any required dilution that can be used in plant protection can be obtained from this concentrate by diluting with water.

Ready-to-use powders are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry garments for seeds.

Extruded granules Active ingredient [Compound of formula (I)] 15%
Sodium lignosulfonate 2%
Carboxymethyl cellulose 1%
Kaolin 82%

The active ingredient is mixed and ground with an auxiliary agent and the mixture is moistened with water. The mixture is extruded and then dried in an air stream.

Coated granules Active ingredient [Compound of formula (I)] 6%
Polyethylene glycol (mol. Wt. 200) 3%
Kaolin 89%

The finely ground active ingredient is uniformly applied to kaolin moistened with polyethylene glycol in a mixer. Coated granules that do not generate powder are obtained in this manner.

Suspension concentrate Active ingredient [Compound of formula (I)] 40%
Propylene glycol 10%
Nonylphenol Polyethylene Glycol Ether (15 mol of ethylene oxide) 6%
Sodium lignosulfonate 10%
Carboxymethyl cellulose 1%
Silicone oil (75% in water emulsion form) 1%
32% water

The finely ground active ingredient is mixed well with the adjunct to give a suspension concentrate, which can be diluted with water to give a suspension of any desired dilution. Such dilutions can be used to treat living plants and plant reproductive materials by spraying, pouring or soaking to protect against microbial eclipse.

Fluid concentrate for seed treatment Active ingredient [Compound of formula (I)] 40%
Propylene glycol 5%
Copolymer Butanol PO / EO 2%
Tristyrene phenol (tristyrenephenole) with 10 to 20 mol of EO 2%
1,2-benzoisothiazolin-3-one (in the form of a 20% aqueous solution) 0.5%
Monoazo pigment calcium salt 5%
Silicone oil (75% in water emulsion form) 0.2%
Water 45.3%

The suspension can be obtained at any desired concentration by homogeneously mixing the finely ground active ingredient with an auxiliary agent to obtain a suspension concentrate and diluting with water. Such dilution can be used to treat and protect living plants as well as plant reproductive materials from microbial ectoparasitism by spraying, pouring or soaking.

The compound of formula (I) in which 28 parts of the slow-release capsule suspension are combined is mixed with 2 parts of an aromatic solvent and 7 parts of a toluene diisocyanate / polymethylene-polyphenyl isocyanate mixture (8: 1). The mixture is emulsified in a mixture of 1.2 parts polyvinyl alcohol, 0.05 parts defoamer and 51.6 parts water until the desired particle size is achieved. To this emulsion is added a mixture of 2.8 parts of 1,6-diaminohexane in 5.3 parts of water. The mixture is stirred until the polymerization reaction is complete.

The resulting capsule suspension is stabilized by adding 0.25 parts of thickener and 3 parts of dispersant. The capsule suspension formulation contains 28% of the active ingredient. Medium capsule diameter is 8-15 microns.

The resulting formulation is applied to the seeds as an aqueous suspension in a device suitable for the purpose.

Examples of Preparation Example 1: This example is N-ethyl-N'-[5-methoxy-2-methyl-4- [2- (trifluoromethyl) tetrahydrofuran-2-yl] phenyl] -N- The preparation of methyl-formamidine (Compound 1.22) is illustrated.

Preparation of N-Ethyl-N'-[5-Methoxy-2-methyl-4- (2,2,2-trifluoroacetyl) phenyl] -N-methyl-formamidine N'-(4-Bromo-5- Methoxy-2-methyl-phenyl) -N-ethyl-N-methyl-formamidine (6.0 g, 21.04 mmol) was dissolved in tetrahydrofuran (84 mL) and cooled to −78 ° C. A 2N n-butyllithium solution in cyclohexane (18.9 mL, 37.87 mmol) was added dropwise. The yellow solution thus obtained was stirred at −78 ° C. for 1 hour. Ethyl 2,2,2-trifluoroacetate (8.97 g, 63.128 mmol) was added dropwise as it was. At the end of the addition, the cooling bath was removed and the reaction was warmed to 0-5 ° C. and then quenched with saturated ammonium chloride solution. The mixture was extracted with ethyl acetate. The organic layer was washed with brine, dried over sodium sulfate, filtered and concentrated under reduced pressure.

The residue was purified by chromatography on silica gel using ethyl acetate / dichloromethane as an eluent system and N-ethyl-N'-[5-methoxy-2-methyl-4- (2,2,2-trifluoro) Acetyl) phenyl] -N-methyl-formamidine (5.1 g, 16.89 mmol) was obtained.
Major isomers: ^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ = 1.27 (t, 3H), 2.22 (s, 3H), 3.08 (s, 3H), 3.41 (d) , 2H), 3.90 (s, 3H), 6.36 (br.s, 1H), 7.56 (br.s, 2H)
Trace isomers: ^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ = 1.27 (t, 3H), 2.22 (s, 3H), 3.08 (s, 3H), 3.62 (d) , 2H), 3.90 (s, 3H), 6.36 (br.s, 1H), 7.50 (s, 1H), 7.56 (br.s, 1H)
Ratio E / Z: 3: 5

Preparation of N-Ethyl-N'-[4- [1-Hydroxy-1- (trifluoromethyl) allyl] -5-methoxy-2-methyl-phenyl] -N-methyl-formamidine N-Ethyl-N' -[5-Methoxy-2-methyl-4- (2,2,2-trifluoroacetyl) phenyl] -N-methyl-formamidine (2.00 g, 6.29 mmol) in a solution of tetrahydrofuran (7 mL). Bromo (vinyl) magnesium (7.23 mL, 7.23 mmol) was added dropwise at −5 ° C. and the reaction mixture was stirred at 0 ° C. for 45 minutes. The reaction mixture was filtered and poured onto chilled water (15 mL), then aqueous ammonium chloride solution was added until the precipitate disappeared and the mixture was extracted with ethyl acetate (3 x 20 mL). The combined organic layers were washed with brine, dried over sodium sulphate, filtered, concentrated under vacuum, N-ethyl-N'-[4- [1-hydroxy-1- (trifluoromethyl) allyl]-]-. 5-Methoxy-2-methyl-phenyl] -N-methyl-formamidine (2.20 g, 5.99 mmol) was obtained. The material was used as a crude product for the next step.
^{1 1} H-NMR (400 MHz, CDCl ₃ ): δ = 7.46 (1H, m), 7.07 (1H, s), 6.42 (2H, m), 6.31 (1H, s), 5 .77 (1H, d), 5.52 (1H, d), 3.93 (3H, br s), 3.36 (2H, m), 3.03 (3H, s), 2.21 (3H) , S), 1.24 (3H, t)

Preparation of N'-[4- [1-allyloxy-1- (trifluoromethyl) allyl] -5-methoxy-2-methyl-phenyl] -N-ethyl-N-methyl-formamidine N-ethyl-N' -[4- [1-Hydroxy-1- (trifluoromethyl) allyl] -5-methoxy-2-methyl-phenyl] -N-methyl-formamidine (2.25 g, 6.13 mmol) N, N- Sodium hydride (0.258 g, 6.74 mmol) was added little by little to a solution of dimethylformamide (24.5 mL). The reaction mixture was stirred at room temperature for 30 minutes. Allyl bromide (0.536 mL, 6.13 mmol) was then added dropwise and the reaction mixture was stirred at room temperature overnight. The reaction mixture was quenched by the slow addition of saturated ammonium chloride solution (20 mL) and then extracted with ethyl acetate (3 x 15 mL). The combined organic layers were washed with water (2 x 100 mL), brine, dried over sodium sulfate, filtered and concentrated under vacuum. The crude material was purified by chromatography on silica gel using ethyl acetate / cyclohexane as an eluent system, and N'-[4- [1-allyloxy-1- (trifluoromethyl) allyl] -5-methoxy-2- Methyl-phenyl] -N-ethyl-N-methyl-formamidine (1.99 g, 5.3 mmol) was obtained.
^{1 1} H-NMR (400 MHz, DMSO): δ = 1.14 (t, 3H), 2.12 (s, 3H), 2.86-3.08 (m, 3H), 3.44 (m, 2H) ), 3.70 (s, 3H), 3.85 (d, 2H), 5.17 (dd, 1H), 5.33 (m, 2H), 5.49 (d, 1H), 5.93 (1H, m), 6.32 (dd, 1H), 6.52 (s, 1H), 7.17 (s, 1H), 7.59-7.86 (m, 1H)

Preparation of N-Ethyl-N'-[5-methoxy-2-methyl-4- [5- (trifluoromethyl) -2H-furan-5-yl] phenyl] -N-methyl-formamidine N'-[ 4- [1-allyloxy-1- (trifluoromethyl) allyl] -5-methoxy-2-methyl-phenyl] -N-ethyl-N-methyl-formamazine (1.00 g, 2.7 mmol) in dichloromethane ( The solution (54.0 mL) was degassed with argon, and then benzylidene-bis (tricyclohexylphosphine) dichlorolutenium (0.113 g, 0.135 mmol) was added. The reaction mixture was stirred at room temperature overnight. The reaction mixture was concentrated under vacuum and then the residue was dissolved in water (60 mL) and acidified with 2M HCl. The mixture was extracted with diethyl ether (2 x 20 mL) and then the aqueous layer was basified with aqueous sodium hydrogen carbonate solution (up to pH 10). The solution was extracted with dichloromethane (3 x 20 mL), the combined organic layers were washed with brine, dried over sodium sulfate, filtered and concentrated under vacuum. The crude material was purified by chromatography on silica gel using ethyl acetate / cyclohexane as an eluent system, and N-ethyl-N'-[5-methoxy-2-methyl-4- [5- (trifluoromethyl)-)-. 2H-Fran-5-yl] phenyl] -N-methyl-formamidine (0.90 g, 2.6 mmol) was obtained.
^{1 1} H-NMR (400 MHz, DMSO): δ = 8.22-8.62 (1H, m), 7.49 (1H, s), 7.14 (2H, m), 6.26-6.69 (2H, m), 4.59-4.92 (2H, m), 3.86 (3H, s), 3.57-3.78 (2H, m), 3.28-3.36 (3H) , M), 2.30 (3H, m), 1.28 (3H, t).

Preparation of N-Ethyl-N'-[5-Methoxy-2-methyl-4- [2- (trifluoromethyl) tetrahydrofuran-2-yl] phenyl] -N-methyl-formamidine (Compound 1.22) N -Ethyl-N'-[5-Methoxy-2-methyl-4- [5- (trifluoromethyl) -2H-furan-5-yl] phenyl] -N-methyl-formamidine (200 mg, 0.58 mmol) The ethanol (6 mL) solution of the above was degassed with argon, and palladium charcoal (0.01869 g, catalyst) was added. The reaction mixture was stirred at room temperature for 4 hours under a hydrogen atmosphere. The reaction mixture was filtered through celite and the filtrate was concentrated under vacuum. The solid was dissolved in water (20 mL) and acidified with HCl until pH 1 was reached. The mixture was extracted with diethyl ether (10 mL) and the aqueous layer was basified with NaHCO3. The mixture was extracted with dichloromethane (3 x 10 mL), the combined organic layers were washed with brine, dried over sodium sulfate, filtered, concentrated under vacuum and N-ethyl-N'-[5-methoxy-2. -Methyl-4- [2- (trifluoromethyl) tetrahydrofuran-2-yl] phenyl] -N-methyl-formamidine (Compound 1.22, 98 mg, 0.29 mmol) was obtained.
^{1 1} H-NMR (400 MHz, DMSO): δ = 7.72 (1H, s), 7.27 (1H, s), 6.48 (1H, s), 3.77 (4H, s), 3. 33 (2H, m), 2.99 (3H, br s), 2.64 (1H, ddd), 2.38 (1H, dt), 2.10 (3H, s), 2.00 (2H, 2H, m), 1.14 (3H, m).

Table E: LC / MS (Liquid Chromatography-Mass Spectrometry) Method Using Physical (LC / MS) Data for Specific Compounds of Formula (I):
(ACQUITY UPLC from Waters, Phenomenex Gemini C18, 3 μm particle size, 110 angstrom, 30 × 3 mm column, 1.7 mL / min, 60 ° C, H ₂ O + 0.05% HCOOH (95%) / CH ₃ CN / MeOH 4 1 + 0.04% HCOOH (5%)-2 min-CH ₃ CN / MeOH 4: 1 + 0.04% HCOOH (5%) -0.8 min, ACQUITY SQD mass analyzer from Waters, ionization method: electrospray (ESI), Polarity: Phenomenex, Capillary (kV) 3.00, Corn (V) 20.00, Extractor (V) 3.00, Source temperature (° C) 150, Desolvent temperature (° C) 400, Corn gas Flow (L / Hr) 60, Desolvent gas flow (L / Hr) 700)).

Biological Example Blumeria gramminis forma stritisi (Elysipe graminis f.sp. ritici) / wheat / leaf fragment prevention (powdery mildew on wheat )
The wheat leaf section cultivar Kanzaler was placed on agar in a multi-well plate (24-well type) and sprayed with a water-diluted compounded test compound. One day after application, the powdery mildew-infected plants were sown with leaf pieces by shaking on a test plate. The sown leaf pieces are incubated in an artificial weather room in a light environment of 24 hours of darkness followed by 12 hours of light / 12 hours of darkness at 20 ° C. and 60% relative humidity to bring the activity of the compound to an appropriate level. When damage caused by the disease appeared on the untreated leaf section for inspection (6 to 8 days after application), it was evaluated as a disease control ratio compared with the untreated one.

The following compounds provided at least 80% pest control at 200 ppm in this study when compared to untreated control leaf pieces with significant disease outbreaks under the same conditions.
1.21 and 1.22

Phakopsora pachyrhizi / Soybean / Leaf fragment prevention (Soybean rust)
A 4-week-old soybean plant is sprayed with a water-diluted formulation of the test compound in a spray chamber. One day after application, leaf pieces are cut from the treated plant and placed on agar in a 24-well plate. The leaf pieces are sown by spraying a spore suspension on the leaf back surface of the leaf pieces. After a 24-36 hour incubation period in a climate cabinet at 20 ° C. and 75% relative humidity in the dark, the leaf pieces are then kept at 20 ° C. for 12 hours light / day and 75% relative humidity. When the appropriate level of disease appears in the untreated test plant (12-14 days after application), the leaf piece area percentage covered by the disease is assessed.

The following compounds provided at least 80% pest control at 200 ppm in this study when compared to untreated control leaf pieces with significant disease outbreaks under the same conditions.
1.21 and 1.22

Puccinia recondita f.sp.trici / wheat / leaf fragment prevention (red rust)
The wheat leaf section cultivar Kanzaler was placed on agar in a multi-well plate (24-well type) and sprayed with a water-diluted compounded test compound. One day after application, the leaf pieces were seeded with a fungal spore suspension. Sowned leaf sections are incubated in a climate cabinet in a 12 hour light / 12 hour dark light environment at 19 ° C. and 75% relative humidity to control the activity of the compound, untreated for damage from appropriate levels of disease. When it appeared on the leaf section for inspection (7 to 9 days after application), it was evaluated as a disease control ratio compared with the untreated one.

The following compounds provided at least 80% pest control at 200 ppm in this study when compared to untreated control leaf pieces with significant disease outbreaks under the same conditions.
1.21 and 1.22

Puccinia recondita f.sp.trici / wheat / leaf piece treatment (red rust)
The wheat leaf slice cultivar Kanzler is placed on agar in a multi-well plate (24-well type). Leaf sections are seeded with a suspension of fungal spores. The plates were stored in the dark at 19 ° C. and 75% relative humidity. The compounded test compound diluted with water was applied 1 day after sowing. Leaf sections are incubated in a climate cabinet in a 12 hour light / 12 hour dark light environment at 19 ° C. and 75% relative humidity to test the activity of the compound for untreated damage from appropriate levels of disease. When it appeared on the leaf section for use (6 to 8 days after application), it was evaluated as a disease control ratio compared with the untreated one.

The following compounds provided at least 80% pest control at 200 ppm in this study when compared to untreated control leaf pieces with significant disease outbreaks under the same conditions.
1.21 and 1.22

Claims (15)

Equation (I)

(During the ceremony,
R ¹ and R ² are either each independently selected from C ₁ -C ₄ alkyl and C ₃ -C ₈ cycloalkyl; or R ¹ and R ² together with the nitrogen atom to which they are attached, Forming a 3- to 6-membered saturated cyclic group;
R ³ is hydrogen, halogen or C ₁ -C ₄ alkyl;
R ⁴ and R ⁵ are either each independently selected from hydrogen and C ₁ -C ₄ alkyl; or R ⁴ and R ^5, together with the carbon atoms to which they are attached, a (C = O) Formed;
X is O, S or NCH ₃ ;
n is 0 or 1;)
Compound or salt thereof, metal complex, stereoisomer or N-oxide. The compound according to claim ^1, wherein R ¹ and R ² are independently C _{1 to} C ₄ alkyl. The compound according to claim 1 or 2, wherein R ³ is a halogen or a C _{1 to} C ₃ alkyl. R ⁴ and R ⁵ are either each independently selected from hydrogen and methyl, or R ⁴ and R ^5, together with the carbon atoms to which they are attached, form a carbonyl group, claim 1 Or the compound according to any one of 3. The compound according to any one of claims 1, 2, 3 or 4, wherein R ¹ and R ² are independently selected from methyl, ethyl and isopropyl, respectively. The compound according to any one of claims 1, 2, 3, 4, or 5, wherein R ³ is fluoro, chloro, or methyl. Claims 1, 2, 3, 4, where R ⁴ and R ⁵ are both hydrogen, or R ⁴ and R ⁵ form a carbonyl group with the carbon atom to which they are attached. The compound according to any one of 5 or 6. The compound according to any one of claims 1, 2, 3, 4, 5, 6 or 7, wherein R ¹ is methyl, ethyl or isopropyl and R ² is methyl or ethyl. The compound according to any one of claims 1, 2, 3, 4, 5, 6, 7 or 8, wherein R ³ is chloro or methyl and R ⁴ and R ⁵ are both hydrogen. R ¹ and R ² are independently selected from methyl, ethyl and isopropyl, respectively;
R ³ is fluoro, chloro or methyl;
R ⁴ and R ⁵ are both hydrogen, or R ⁴ and R ⁵ form a carbonyl group with the carbon atom to which they are attached;
X is O, S or NCH ₃ ;
n is 0 or 1,
The compound according to claim 1, or a salt, metal complex, stereoisomer or N-oxide thereof.

N-Ethyl-N'-[5-Hydroxy-2-methyl-4- [2- (trifluoromethyl) tetrahydrofuran-2-yl] phenyl] -N-methyl-formamidine;

N'-[5-Hydroxy-2-methyl-4- [2- (trifluoromethyl) tetrahydrofuran-2-yl] phenyl] -N-isopropyl-N-methyl-formamidine;

N'-[2-Chloro-5-Hydroxy-4- [2- (trifluoromethyl) tetrahydrofuran-2-yl] phenyl] -N-ethyl-N-methyl-formamidine;

N-Ethyl-N'-[5-Hydroxy-2-methyl-4- [4-oxo-2- (trifluoromethyl) tetrahydrofuran-2-yl] phenyl] -N-methyl-formamidine;

N-Ethyl-N'-[5-Hydroxy-2-methyl-4- [2- (trifluoromethyl) tetrahydrothiophene-2-yl] phenyl] -N-methyl-formamidine; or

N-Ethyl-N'-[5-Hydroxy-2-methyl-4- [2- (trifluoromethyl) oxetane-2-yl] phenyl] -N-methyl-formamidine;
The compound according to claim 1, or a salt, metal complex, stereoisomer or N-oxide thereof selected from the above. The compound according to any one of claims 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, wherein X is O or S. A composition comprising a compound of formula (I) as defined in any of claims 1-12 in an amount effective for bactericidal and fungal killing. The composition according to claim 13, further comprising at least one additional active ingredient and / or diluent. A method for exterminating, preventing or controlling phytopathogenic fungi, which is sterilized by phytopathogenic fungi, habitats of the phytopathogenic fungi, plants susceptible to damage by phytopathogenic fungi, or their breeding materials. The compound of the formula (I) defined in any of claims 1 to 12 in an amount effective for killing fungi, or any of claims 1 to 12 in an amount effective for sterilizing and killing fungi. A method comprising applying a composition comprising a defined compound of formula (I).